Process for treating hydrocarbons



Patented Feb. 24, 1942 PROCESS FOR TREATING HYDROOARBONS Russell P.Dunmire, Shaker-Heights, Ohio, as-

signor to The Buckeye poration of Ohio No Drawing.

Laboratories, Inc., a cor- Application August 25, 1941, Serial No,408,260

- .14 Claims. (01.196-16) My invention relates generally to thetreatment of hydrocarbons and has for one of its objects the refining orthe re-refining of suc materials.

The present patent application is a continuation in part of mycopendingpatent application,

. Serial No. 241,960, filed November 23, 1938.

More specifically my invention relates to the treatment of oils such asmineral oils of a lubrieating nature or of an insulating nature, andmineral waxes, etc., all of which are subject to more or lessdeterioration when exposed to air, moisture, metals or other agentswhich cause contamination such as oxidation, polymerization, etc. aswell as contamination by solid materials in suspension.

In the case of lubricating oils, for example, it has been found thatalthough the most modern methods are used in the refining of these oilsfor lubricating purposes yet certain undesirable properties remain inshould be removed. It is known also that in use, lubricating oils aresubject to contamination by water, free and in solution, metallicparticles,

dust and other solids and air both free and dissolved. It has beendiscovered, also, that varying shock loads detrimentally afiect. suchoils. Under such trying conditions many materials such lubricants xwhichcarbon in suspension and precipitated; carbon is also precipitated onthe terminals and oil gases and hydrogen are produced as well as someun.- saturates. V The effect of this israpid oil deterioration from thearc, carbonization of the oil, decreased rupture capacity, explosionhazard v and possible failure of the breaker. In the case of electrictransformers, water, gas in solution, organic fluids and volatiles,organic acids, sludges, resinous bodies and compounds, tars, pitches andoxyasphaltic compounds are produced due to the heat from operation ofthe transformer. This, of course, lowers the insulation value of theoil, prevents proper heat dissipation, induces gas pocket formation,creates explosion hazards and volatile corrosion, promotes power factorlosses and possible failure of the equipment. I might say that in thecase of oil-insulated electric cables the high electric stresses due tooperation "of the cable causes deterioration of the insulating oil inmuch the same fashion as in the case of transformers, the effect ofwhich may be failure of the cable due to ionization, wax formation, adecrease in resistivity and an increase in the power factor. In the caseof mineral waxes I have found that the products of oxidation togetherwith free water and dissolved gases producediscoloration are produced inthe oil which deleteriously affect the same so far as itsuse as alubricant is concerned.

Without attempting to exhaust the subject, I might say that thesecontaminants produce sludges due to excessive heating, free andamorphous carbon, stable and unstable emulsions, polymerizationproducts, soluble and insoluble resins and gums, acids, metallic soap,asphaltic sludges; free acids, dissolved gases and free water as well asaddition agents are present in the oil. The oil also becomes discolored'So far as a lubricating oilis concerned, the presence of these variousmaterials inthe oil causes excessive bearing wear, over-heated bearings,increases internal oil friction, reduces the film strength, etc.

Insulating oils are subjected to contamination and deterioration as theresult of contact of the heated hydrocarbon with air or certain other ofthe mineral wax and in many cases liberates unsaturated compounds andforms insoluble resins, gums, soaps and various types of sludgeimpurities. the type of mineral wax.

The present inventionprovides a process for the removal of theimpurities or contaminants above referred to.

My process, it is to be-noted, may be continuous or intermittent.

Broadly speaking, myimproved process is directed to the treatment of theoils and waxes above referred to wherein I agitate a mixture of the oilor wax to be treated and an adsorbent material while the mixture is atan elevated tem-v perature and under vacuum. After this treatment themixture is filtered.

More specifically, in practicing my invention a the material to betreated is introduced into a heating and mixing chamber which ishermetically sealed and connected to any .suitable commercial typefractional condenser. A suitable adsorbent material, such as bone char,carbon black, fullers earth, etc., is added to the charging stock in theheating and mixing chamber. The amount of adsorbent material employed sofar as maximum amount is concerned is not These vary slightly in degreewith to the mixing and heating chamber.

thermal decomposition or deterioration, the heat-' critical'except.perhaps for economical reasons.

For example, I may add from one-half per cent to twelve per cent, oreven as high as forty per cent in special cases, by weight of the oil orwax being treated or processed. In addition to the adsorbent material Iprefer to add water and in some cases superheated steam as a flushingagent and an alkali such as, potassium hydroxide or calcium hydroxide orthe like to bring about saponification of any' residual acid which ispresent and which is prgbably due to oxidation of the oil or wax due tocontact of the heated material with air. I have found that this residualacid is not readily adsorbable by the adsorbent material of the mixture.The addition of the potassium hydroxide saponifies this acid as abovementioned so that the same may be readily removed.

The amount of water and alkali added may be varied within a wide range.For example, I

\ may saythat theamount of water or steam added may also be accomplishedduring treatment and while in the presence of adsorbent materials whichmay or may not have some definite action as catalysts.

For example, in the treatment of certain mineral waxes I am able toproduce a pure white wax which may be used in the manufacture ofartificial honeycombs from which all traces of odor are removed. In thecase of electrical insulating oils the high vacuum accelerates theremoval of the free water of solution as well as all gases with whichthe oil may be saturated and which woulddeleteriously affect theelectrical and physical characteristics of this class of oil.

may-vary between one-quarter of a pound and.

After' this treatment of the material in the heating and mixing chamberI pass the material through a filter in a closed filter chamber..Various forms of filter materials maybe employed.

.For' example, I paper, glass cloth, glass wool or metallic screens, anyor allof which may be pro,- tected with a'diatomaceous filter aid, so asto secure the maximum degree of clarity of the ma "terial being treated.The material may be driven pump or a turbine impellor while the mixtureis being raised to an elevated temperature in a range suflicient todrive off the water and the low boiling point volatile impurities. Thetemperature range extends up to a value in the neighborhood of the flashpoint of the oil or wax in its finally treated state and includes anelevated temperature below the flash point of the finally H treated oilor wax and preferably embraces a range 'of approximately 50 to 150degrees F. below the flash point of the finally treated oil or wax. Itwill beappreciated, of course, that at such a temperature the water,light ends and volatile oxidation products will be driven off and flowinto the condenser which, as above noted, is connected.

Because of ing of the mixture at a temperature substantially I beyondthefiash point of the finally treated oil or wax causes a materialreduction in the yield of the oil or wax being treated. At temperaturesbelow the flash point of the finally treated oil or wax, the yield isgood, but as the temperature substantially exceeds the flash point ofthe finally treated oil or wax, the yield rapidly-decreases, renderingthe process uneconomical.

The mixture is maintained at this elevated temperature and subjected toagitation for from fifteen minutes to an hour, for example.

As above mentioned. I prefer to employ a vacuum on the heating andmixing chamber, although good results are obtained without theemployment of a vacuum. If a vacuum isemployed I prefer a high vacuumfrom twenty-eight to thirty inches of mercury as referred to a thirtyinch barometer at 'sea level. The purpose ofutilizinga vacuum is toincrease' the rate of distillation at a lower temperature of. oils whichare quitesensitive to cosity.

1 The above remarks apply also .to the treatment of mineral waxes. Fr 1H-ydr'ogenization of the liquids being treated the action ofheat,.especia'lly those. of a low vispumped through the filter ordrawnthrough.

It will be understood thatin the filtering op.- eration the adsorbentmaterialwith it adsorbed impurities such, as resins,,; inetallicsoaps,heavy residual acids, .polymer'products. mechanical impurities, etc areremoved The treated material. W.-- tion suitable for. use or service.

- a' cleancondi- .It win. beseen-ffrom "all of the foregoing that thepresent-invention provides a process for the treatment pf oils-andwaxes, whereby contam-- inants in 'these' materials which deleteriouslyfeet the same are removed, the process being adapted for use inconnection "with the refining-1" of such oils and waxes as well as to,the re-re'-, r fining of the sameafter they have beenin'servicaf r Thespecification and the claims are directedito .a .process for removingimpuritiesfrornqa con taminated or used mineral substance :of th'eclass" consisting of mineral oils andjmineral fwaxes.

The term contaminatedfias' ii sedxherein means an oil or wax whichisuniitlfor-aspecific purpose. Itis to be understoodggo'fcourse,'thatchanges may be made in.- theprocedures above, described withoutdeparting from;; the"spirit and scope of my invention.

I claim as my invention:

1.- Theprocess for removing impurities froma contaminated or usedmineral substance of the class consisting of, mineral oils and mineralwaxes.

which process comprises mechanically mixing and agitating thecontaminated or used mineral substance'and a' solid adsorbent materialin a sealed containerv to adsorb the high boiling point impurities,heating the mixture of the mineral substance being treated and thesolidadsorbent material in the sealed container under vacuum at atemperature in the'range of approximately 50 to degrees F. below theflash point of the finally treated mineral substance to drive off thewater and the low boiling point volatile impurities, and

separating the adsorbent material with its adsorbent impuritiesfromthe'rnineral substancebeing treated to recoverthelatter.

2. The process for removing impurities from a contaminated or usedmineral oil, which'pr'ocess I comprises mechanically mixing andagitating the contaminated-caused oil and a solid adsorbentmaterialin-asealed container to adsorb the high boiling ,pointimpurities, heating the mixture of the" oil'being treated and the solidadsorbent marterial the sealed container under vacuum at a Tli 50 to 150degrees F. below theflashzpoint of the i the latter.

v to recover the latter.

, eral substance being treated and the solid ad;

v vacuum at a temperature below the flash point 1 comprisesmechanicallymixing and agitating the contaminated or used oil anda solidadsorbent treated oil to drive off the'water and the low boi-lmaterialin a sealed container to adsorb the high ing point volatile impurities,and separatingthe boiling po nt impuri s, heating he mixture ofadsorbent material with its adsorbed impurities 5 the Oil being treatedand thz solid adsorbent mafrom the oil being treated to recover thelatter. rial in t e sea ed con ainerunder. vacuum a a 3. The process forremovingimpuritiesefrom a mp r ure elow the h p n f h n l y contaminatedor used mineral wax. which-process treated Oil drive Off the Water a elow comprises mechanically mixing and agitating the boiling PointVolatile impurities, and Separating temperaturein the range of:approximatelytfl to 150 degrees F. below the flash point of the finallycontaminated or used wax, and a solid adsorbent the adsorbent materialwith its adsorbed impuri? ties from the oil being treated to recover thematerial in a sealed container-to adsorb the high latter,

boiling point impurities, heating the mixture of the wax being treatedand, the solid adsorbent material in the sealed container: ,under vacuumcontaminated or usedimiheraliwax, w i p ess at a temperature in therange. of approximately comprises mechanicallym n n agitating thecontaminated or used wax. 'and'a solid adsorbent material in a sealedcontainerto adsorb the high finally treated wax to drive-01fthew'ateriand the v boiling point impurities, heating the mixture of.

low boiling point volatile i'mpurities, and separating the adsorbentmaterialwith itsdads'orbedimpurities from the wax being 4. Theeprocessfor remo n Purities froma contaminated or used mne oil,l,whichg"'processcomprises mechanically m in nd agitatin'g the contaminated or used/o 1aolid'jiadsorbent ma p es. m the W "terial, an alkali, and ari e. eousmedium of the v classeconsisting of water and steamfinfa sealed T p c sf0 container to adsorb the gh boiling point im- I a a purities, heatingthejfm -xturecort e oii beingpr se m amca ly e si s t e treated, theadsorbentfmaterial; the alkali and centaminetedior iised as i ads n ia-i the aqueous medium i'n'fthe sealed container. un-r teriel; an l i -dantique-011$ l l t class consisting or. water and steam in a-sealed dervacuum at a temperature infthe range of ap-g v v t H proximately to 150degrees F..be1ow the flash o iner to adso b t i h b ns point mypurities,heating themixture ofi the oil being point of the finally treatedjoil.to drive of! the v i water and the low boiling pointivolatil'eil'npuri35- t e d-th adsorbent mat ial. t e alkaliand ties, and separatingtheadsorbent material with the 11111180115 di imt l n r- 3 1 itsadsorbed impuritiesfro'm the oil being treated a m e -J-a temperature;below the ifl 1 point-of vtheflnistlly treated ;;oil in drive off the 5.The process forfremoving impurities from a class consisting of mineraloils and mineral waxes, which process comprises mechanically mixing andagitating the contaminated or used" mineralsubstance, a solid adsorbentmaterial I I r and an aqueous medium of the class consisting 1 5 1 e i t0f i h e and mineral Wa of water and steam, in a sealed' container toad- .wh c r c s wm ises m c a cal y i sorb the high boiling pointimpurities,, heating r insn l',ieei h is the contaminated or "used-mnthe mixture of the mineralsubstance beingtreah 'i' t he. o id.adsorbent materi and an ed, the solid adsorbent material and theagu'eousmedium in the sealed container under vacuum a ed to recover the latte'r.

water and the low boiling point volatile imp ties, and separating the aorben'tmaterial" its adsorbed impurities ;fr'om the rni' f stance beingtreated toirec'oyerj 6'. The process fori-emoving' contaminated orusedmin class consisting of' inine'ra I waxes, which process comprisesmec'hanically 1 mixing and agitating thecon'tamihated or used mineralsubstance and=a solid adsorbent material in a sealed container: toadsorb the high boiling in point impurities, heating the mixture of-themin- 05 and ag tating the coir subs'tance', a solid has) and anaqueou's'm n a sealed container to adsorb separating-theladsorbent matrial with its adsorbed impurities-1mm the mineral substance beingtreatedto'grecover the latter.

. 1 1 The procession re sorbent material in the sealed container under IJ of the finally treated mineral substance to drive- 7 the high "be hwith its adsorbed impurities from themineral substance being treated torecover the latter.

7. The process for removingimpurities from a ous'mediumlin' the sealedcontainer under vacuum at altemperature in the range of 50 to,150

'degree's F; below the flash pointof the finely contaminated or usedmineral oil,which; process treated oil to drive oil the water and thelow 8. The process for removing impurities from a the wax being treatedand the so1id;adsorbent: t t recover 20 material in the sealed containerunder vacuum .at a temperature'below the flash point of the finallytreated wax to drive- 01i the water -and'the purities, and separatmoving impuritiesfrom :a I contaminated or used'mineralcil, whichprocess water and the jlow' boiling point volatile impuri-' contaminatedor used mineral substance of the 40 T a epa th adsbrbent er l; h:

,1 its adsorbentiimpurities-from the oilflbeing treat f.

. (10. Theyprocess for removinginipuritiesffrom, a contaminated or usedi'mineral substance of the-1 in the sealed container-under vacuum at atem-f per-ature j below: the hash point [of the finally treatedinineralsubstance to driveeoff the water moviiigimpurities from a H I v h gpoint impurities, heating'the off the water and the low boiling pointvolatile) mixture;oif',the;mineral substance being treated,

, impurities, and separating the adsorbent material theyaq bgm mat i l,t lk and t boiling point volatile impurities, and separating theadsorbent material with its adsorbed impurities tromthe mineralsubstance being treated to recover the latter.

12. The process for removing impurities from a contaminated or usedmineral substance 01 the class consisting of mineral oils and mineralwaxes, which process comprises mechanically mixing and agitating thecontaminated or used mineral substance, a solid adsorbent material, analkali, and an aqueous medium or the class consisting of water and steamin a sealed container to adsorb the high boiling point impurities,heating the mixture of the mineral substance being treated, theadsorbent material, the alkali and the aqueous medium in the sealedcontainer under vacuum at a temperature below the flash point of thefinely treated oil to drive off the water and the low boiling pointvolatile impurities, and separating the: adsorbent material with itsadsorbed impurities from the mineral substance being treated to recoverthe latter.

13. The process for removing impurities from a.

, contaminated or used mineral wax, which process comprises mechanicallymixing and agitating the contaminated or used wax, a solid adsorbentmaterial. an alkali, and an aqueous mediums! the class consisting ofwater and steam in a sealed container to adsorb the high boiling. point-,im-

purities, heating the mixture of .the wax being treated, the adsorbentmaterial, the alkali'and the aqueous medium in the sealed container un-'der vacuum at a temperature in the range of approximately 50 to 150degrees F. below the flash point of the finally treated wax to drive of!the water and the low boiling' point volatile impurities, and separatingthe adsorbent material with its adsorbed impurities from the wax beingtreated to recover the latter.

14. The process for removing impurities from a contaminated or usedmineral wax, which process comprises mechanically mixing and agitatingthe contaminated or used wax, a solid adsorbent material, an alkali, andan aqueous medium or the class consisting of water and steam in a sealedcontainer ,to adsorb the high boiling point impurities, heating themixture of the wax being treated, the-adsorbent material, the alkali andthe aqueous inedium in the sealed container under vacuum' at atemperature below the flash point of the finally treated waxto drive offthe water and the low boiling point volatile impurities, and separatingthe adsorbent material with its adsorbed impurities from the waxbeingtreated to recover the latter.

RUSSELL P. DUNMIRE.

